Desenvolvimento de um novo complexo macrocíclico do sistema cobalto cyclam

In this work were synthesized and studied the spectroscopic and electrochemical characteristics of the coordination compounds trans-[Co (cyclam)Cl2]Cl, trans- Na[Co(cyclam)(tios)2], trans-[Co(en)2Cl2]Cl and trans-Na[Co(en)2(tios)2], where tios = thiosulfate and en = ethylenediamine. The compounds were characterized by: Elemental Analysis (CHN), Absorption Spectroscopy in the Infrared (IR), Uv-Visible Absorption Spectroscopy, Luminescence Spectroscopy and Electrochemistry (cyclic voltammetry). Elemental Analysis (CHN) suggests the following structures for the complex: trans- [Co(cyclam)Cl2]Cl.6H2O and trans-Na[Co(cyclam)(tios)2].7H2O. The electrochemical analysis, when compared the cathodic potential (Ec) processes of the complexes trans- [Co(cyclam)Cl2]Cl and trans-[Co(en)2Cl2]Cl, indicated a more negative value (-655 mV) for the second complex, suggesting a greater electron donation to the metal center in this complex which can be attributed to a greater proximity of the nitrogen atoms of ethylenediamine in relation to metal-nitrogen cyclam. Due to the effect of setting macrocyclic ring to the metal center, the metal-nitrogen bound in the cyclam are not as close as the ethylenediamine, this fact became these two ligands different. Similar behavior is also observed for complexes in which the chlorides are replaced by thiosulfate ligand, trans-Na[Co(en)2(tios)2] (-640 mV) and trans-Na[Co(cyclam)(tios)2] (-376 mV). In absorption spectroscopy in the UV-visible, there is the band of charge transfer LMCT (ligand p d* the metal) in the trans-Na[Co(cyclam)(tios)2] (350 nm, p tios  d* Co3+) and in the trans-Na[Co(en)2(tios)2] (333 nm, p tios d* Co3+), that present higher wavelength compared to complex precursor trans- [Co(cyclam)Cl2]Cl (318 nm, pCl  d* Co3+), indicating a facility of electron density transfer for the metal in the complex with the thiosulfate ligand. The infrared analysis showed the coordination of the thiosulfate ligand to the metal by bands in the region (620-635 cm-1), features that prove the monodentate coordination via the sulfur atom. The νN-H bands of the complexes with ethylenediamine are (3283 and 3267 cm-1) and the complex with cyclam bands are (3213 and 3133 cm-1). The luminescence spectrum of the trans-Na[Co(cyclam)(tios)2] present charge transfer band at 397 nm and bands dd at 438, 450, 467, 481 and 492 nm.

Síntese, caracterização e estudo fotofísico de complexos de 4,4- diaminoestilbeno-2,2-dissulfonato com íons lantanídeos

This is a work involving fundamental studies of chemistry where the synthesis and structural characterization, as well as a possible future application of these new compounds as luminescent sensors or sunscreen agents, complexes with 4,4 diaminostilbene-2,2-disulfonic (DSD) and trivalent lanthanide ions La3+, Nd3+, Eu3+, Gd3+ and Yb3+, were synthesized in the ratio of 3 mmol: 1 mmol (DSD: lanthanides). The complexes obtained with these ions were present in powder form and were characterized by complexometric titration with EDTA CHN Elemental analysis, molecular absorption spectroscopy in the ultraviolet region, the absorption spectroscopy in the infrared, thermal analysis (TG / DTG), Nuclear Magnetic Resonance - NMR 1H and Luminescence Spectroscopy. The complexometric titration and CHN analysis, confirmed the TG / DTG which suggest that these complexes have the following general chemical formulas: [La2(C14H12S2O6N2)2(H2O)2Cl2].7H2O,[Nd2(C14H12S2O6N2)2(H2O)2Cl2].6H2O,[Eu2(C14 H12S2O6N2)2(H2O)2Cl2].7H2O,[Gd2(C14H12S2O6N2)2(H2O)2Cl2].4H2O e [Yb2(C14H12S2O6N2)2(H2O)2].6H2O. The disappearance of the bands in the infrared spectrum at 2921 cm-1 and 2623 cm-1 and the displacement of the bands in the spectra of the amine complex indicate that the lanthanide ion is coordinated to the oxygen atoms and the sulfonate groups of the nitrogens amines, suggesting the formation of the dimer. The disappearance of the signal and the displacement signal SO3H amines in the 1H NMR spectrum of this complex are also indicative coordination and dimer formation. The Thermogravimetry indicates that the DSD is thermally stable in the range of 40º to 385°C and their complexes with lanthanide ions exhibit weight loss between 4 and 5 stages. The Uv-visible spectra indicated that the DSD and complexes exhibit cis isomers. The analysis of luminescence indicates that the complexes do not exhibit emission in the region of the lanthanides but an intense emission part of the binder. This is related to the triplet states of the ligand, which are in the lowest energy state emitting lanthanide ions, and also the formation of the dimer that suppress the luminescence of ion Eu3+. The formation of dimer was also confirmed by calculating the europium complex structure using the model Hamiltonian PM6 and Sparkle

Estruturas tectônicas cenozóicas na porção leste da Bacia Potiguar - RN

This thesis encompasses the integration of geological, geophysical, and seismological data in the east part of the Potiguar basin, northeastern Brazil. The northeastern region is located in South American passive margin, which exhibits important areas that present neotectonic activity. The definition of the chronology of events, geometry of structures generated by these events, and definition of which structures have been reactivated is a necessary task in the region. The aims of this thesis are the following: (1) to identify the geometry and kinematics of neotectonic faults in the east part of the Potiguar basin; (2) to date the tectonic events related to these structures and related them to paleoseismicity in the region; (3) to present evolutional models that could explain evolution of Neogene structures; (4) and to investigate the origin of the reactivation process, mainly the type of related structure associated with faulting. The main type of data used comprised structural field data, well and resistivity data, remote sensing imagery, chronology of sediments, morphotectonic analysis, x-ray analysis, seismological and aeromagnetic data. Paleostress analysis indicates that at least two tectonic stress fields occurred in the study area: NSoriented compression and EW-oriented extension from the late Campanian to the early Miocene and EW-oriented compression and NS-oriented extension from the early Miocene to the Holocene. These stress fields reactivated NE-SW- and NW-SE-trending faults. Both set of faults exhibit right-lateral strike-slip kinematics, associated with a minor normal component. It was possible to determine the en echelon geometry of the Samambaia fault, which is ~63 km long, 13 km deep, presents NE-SW trend and strong dip to NW. Sedimentfilled faults in granite rocks yielded Optically Stimulated Luminescence (OSL) and Single-Aliquot Regeneration (SAR) ages at 8.000 - 9.000, 11.000 - 15.000, 16.000 - 24.000, 37.000 - 45.500, 53.609 - 67.959 e 83.000 - 84.000 yr BP. The analysis of the ductile fabric in the João Câmara area indicate that the regional foliation is NE-SW-oriented (032o - 042o), which coincides with the orientation of the epicenters and Si-rich veins. The collective evidence points to reactivation of preexisting structures. Paleoseismological data suggest paleoseismic activity much higher than the one indicated by the short historical and instrumental record

Tecttôniica póss--riifftte na Baciia Pottiiguar

The study of Brazilian sedimentary basins concentrates on their rift phase, whereas the Post-rift phase has been considered a tectonic quiescent period. The post-rift sequence of the Potiguar Basin, in the far northeastern Brazil, was once considered little deformed, however several studies have shown how that it was affected by major fault systems. The purpose of this thesis is to characterize the post-rift tectonic. The specific objectives are: to characterize the Neogene and Quaternary sedimentary units that outcrop of the Potiguar Basin; to show how the NW-SEtrending Afonso Bezerra Faults System deformed outcrop rocks in the Basin; to describe soft-sediment deformation in gravels of the Quaternary Alluvial Deposits from Açu River. Facies analyses, grain-size studies, luminescence dating, remote sensing, structural mapping, shallow geophysics (georadar), paleostress and petrography were carried out. The structural mapping and the georadar sections indicated that the Carnaubais and Afonso Bezerra fault systems formed fractures, silicified and non-silicified faults or deformation bands, affecting mainly the Açu, Jandaíra and Barreiras formations. The petrographic data indicate that the strong silicification resulted in a sealant character of the faults. Paleostress analysis indicates that two stress fields affected the Basin: the first presented N-S-trending compression, occurred from the Neocretaceous to the Miocene; the second stress field presents E-W-trending compression, acts from the Miocene to the present. It was verified once the Afonso Bezerra System Faults was reactivated in periods post-Campanian and affects all post-rift lithostratigraphic units of Potiguar Basin, including Quaternary sedimentary covers. The study about soft-sediment deformation structures indicates that they are similar in morphology and size to modern examples of seismically-induced deformation strutures in coarse sediments. TL and OSL ages indicate that sediment deposition and associated soft-sediment deformation occurred at least six times from ~352 Ka to ~9 Ka. Finally these studies demonstrate how recent is tectonics in the Basin Potiguar

Geomorfologia e neotectônica no Vale do Apodi-Mossoró RN

Numerous studies have indicated that the Potiguar Basin is affected by Cenozoic tectonics. The reactivation of Cretaceous fault systems affect the post-rift units, witch include Neogene and overlying Quaternary sediments. In this context, the objectives of this thesis are the followings: (1) to characterize the effects of post-rift tectonics in the morphology of Apodi Mossoró-river valley located in the central portion of the Potiguar, (2) to characterize the drainage of the Apodi Mossoró river valley and investigate the behavior of their channels across active faults, and (3) to propose a geologic-geomorphological evolutionary model for the study area. This study used a geological and geomorphological mapping of the central part of the basin, with emphasis on the Quaternary record, luminescence dating of sediments, and geoelectric profiles of the area. The results reveal by maps of structural lineaments and drainage channels of the rivers form valleys that are affected by faults and folds. In Apodi-Mossoró valley, anomalies of channel morphology are associated with the deformation of the post-rift basin. These anomalies show the reactivation of major fault systems in the Potiguar Basin in Cenozoic. On a regional scale, can be seen through the vertical electric profiles that the Cenozoic tectonics is responsible for the elevation of a macro dome NE-SE-trending 70-km long and 50km wide and up to 270 above sea level. In this sector, the vertical electric profiles data show that the contact between the Cretaceous and Neogene rise more than 100m. This Is an important feature of inversion data obtained in this work showed that the deposits that cover the macro dome (Serra do Mel) have ages of 119 ka to 43 ka. In the river valley and surrounding areas Apodi-Mossoró ages vary between 319 ka and 2.7 ka. From these data it was possible to establish the correct geochronological posiconamento paleodepósitos of distinguishing them from the fluvial deposits of the Neogene (Barreiras Formation)

Estudo da decomposição térmica de oxalato de estrôncio dopado com cério(III) como precursor de materiais luminescentes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

TL, OSL and C-14 dating results of the sediments and bricks from mummified nuns' grave

Este artigo apresenta os resultados de datação por TL e OSL de solos, e fragmentos de tijolos de um túmulo, que foi ocupado por duas freiras mumificadas encontradas no Mosteiro da Luz, localizado no Estado de São Paulo, Brasil. As idades encontradas por TL e OSL foram comparadas às obtidas a partir de C-14 dos colágenos contidos em amostras de osso das múmias. A maioria das idades obtidas são do século XVIII. A espectroscopia de radiação-gama foi utilizada para avaliar concentrações de radioisótopos naturais nas amostras e para calcular as taxas de dose anual que resultaram em 3,0 a 5,3 Gy/kano. As concentrações radioativas são próximas daquelas obtidas através de Análise por Ativação de Nêutrons. Os conteúdos de elementos U, Th e Ce são superiores aos encontrados na maioria dos sedimentos.

Desenvolvimento e caracterização de dispositivos luminescentes híbridos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Desenvolvimento e caracterização de dispositivos de visualização eletroluminescentes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudos de absorção e emissão de UV/Vis em xerogéis de sílica dopados com cromo obtidos por processo Sol-Gel

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudos das propriedades ópticas e térmicas dos xerogéis de sílica dopados com Rodamina B

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo das propriedades elétro-óptica de dispositivos eletroluminescentes confeccionados com um compósito híbrido

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Interação do complexo luminescente [Eu(tta)3] com sílica mesoporosa

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Caracterização dos ambientes deposicionais na bacia do Ribeirão Entupido, complexo alcalino do Passa Quatro, estado de São Paulo

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Desenvolvimento e aperfeiçoamento de protocolos de conjugação de nanomarcadores luminescentes com sistemas biológicos para aplicação em imunoensaios

Pós-graduação em Química - IBILCE